Plasmon photocatalysis

ABSTRACT

Plasmons on a waveguide may deliver energy to photocatalyze a reaction.

TECHNICAL FIELD

The present application relates, in general, to plasmons andphotocatalysis.

SUMMARY

A waveguide or other approach may deliver plasmon energy to induce,change the rate of, or otherwise affect a chemical reaction, such as aphotocatalytic reaction. In one embodiment, a waveguide includes aconductive layer that converts electromagnetic energy into plasmonenergy. A portion of the waveguide and/or the conductive layer may havevariations configured to produce and/or support plasmons. In oneembodiment, the waveguide is incorporated in a system that may includean energy source and/or elements configured to direct and/or focus theenergy.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 a shows a waveguide with a conductive layer, a plasmonpropagating on the outer surface of the conductive layer, and aphotocatalyst in the field of the plasmon.

FIG. 1 b shows a waveguide with an outer conductive layer, a plasmonpropagating on the outer surface of the conductive layer, and a defecton the conductive layer that converts plasmons into electromagneticenergy.

FIG. 1 c shows a photocatalyst with energy incident on it, having a bandgap between energy levels.

FIG. 1 d shows a bent fiber waveguide with a particle near the bend anda photocatalyst near the particle.

FIG. 2 a shows a vessel with material and a waveguide, where a laseremits electromagnetic energy that is reflected from a mirror into thewaveguide.

FIG. 2 b shows the vessel with material after photocatalysis.

FIG. 2 c shows a laser with a fiber that extends over a long distance toa vessel with a material in it.

FIG. 3 a shows a source of electromagnetic energy, a mirror, and avessel that holds an array of waveguides, where the electromagneticenergy reflects off the mirror into the wave guides.

FIG. 3 b shows a top view of the array of waveguides.

FIG. 4 shows a waveguide that is partially covered with a conductivelayer.

FIG. 5 shows a waveguide that has a conductive layer, a dielectriclayer, and a photocatalyst layer, where the waveguide is near aninteraction material.

FIG. 6 shows a waveguide having a conductive layer with an aperture,where the aperture is bordered by a grating.

FIG. 7 shows a waveguide with a periodic array of conductive material.

DETAILED DESCRIPTION

Methods for interacting electromagnetic energy with matter are known;for example, in U.S. Pat. No. 4,481,091 entitled CHEMICAL PROCESSINGUSING ELECTROMAGNETIC FIELD ENHANCEMENT to Brus, et al., which isincorporated herein by reference. Specifically, electromagnetic energymay be delivered to a spatial position in order to induce aphotocatalytic reaction, as described in U.S. Pat. No. 5,439,652entitled USE OF CONTROLLED PERIODIC ILLUMINATION FOR AN IMPROVED METHODOF PHOTOCATALYSIS AND AN IMPROVED REACTOR DESIGN to Sczechowski, et al.,which is incorporated herein by reference.

Further, electromagnetic energy may be delivered to a given area usingsurface plasmons. Surface plasmons have been used as sensors, asdescribed in J. Homola, S. S. Yee, and G. Gauglitz, “Surface plasmonresonance sensors: review”, Sensors and Actuators B, Volume 54, 1999,3-15, which is incorporated herein by reference. One type of surfaceplasmon resonance sensor uses optical waveguides. In this technique,electromagnetic energy propagates down a metal-coated waveguide, aportion of the electromagnetic energy couples to an evanescent wave inthe metal coating, and the evanescent wave couples to plasmons on theouter surface of the metal. Surface plasmons may exist on a boundarybetween two materials when the real parts of their dielectric constantsε and ε′ have different signs, for example between a metal and adielectric.

In a first embodiment, shown in FIG. 1 a, a waveguide 102 includes anouter conductive layer 104. Electromagnetic energy 106 is coupled intothe waveguide 102 and propagates in the waveguide 102. Thiselectromagnetic energy couples to an evanescent wave in the conductivelayer 104, which couples to a plasmon 113 on an outer surface 108 of theconductive layer 104. The conductive layer 104 forms a boundary with aninteraction material 10. The conductive layer 104 may be a highconductivity metal such as silver, gold, or copper, or it may be anothertype of metal or conductive material. The waveguide may be an opticalfiber, a 2d dielectric slab waveguide, or another kind of waveguide.Metal-coated fibers are known to those skilled in the art and variousmethods exist for coating a fiber with metal, including vacuumevaporation and sputtering.

In one embodiment, a chemical reaction is induced by the plasmons 113.In one embodiment, the chemical reaction is a photocatalytic reaction.In this embodiment, the interaction material 110 may include aphotocatalyst 112. Plasmon energy may be delivered to the photocatalyst112 by placing the photocatalyst 112 substantially in the field of theplasmon 13. Plasmon energy may also be delivered to the photocatalyst bycausing the plasmon 113 to radiate electromagnetic energy 115, forexample by forming a defect 114 on the surface of the conductive layer,as shown in FIG. 1 b. Although the defect 114 in FIG. 1 b is shown asextending from the conductive layer 104, in other embodiments the defectmay be a deficit of material, may include material or defect integral tothe conductive layer 104, material that is not in intimate contact withthe conductive layer 104, or any other material or structure known toproduce electromagnetic energy responsive to plasmon energy.

Although the outer layer 104 is described as a conductive layer in theexemplary embodiments of FIGS. 1 a and 1 b, it is not necessary for thelayer 104 to be conductive for plasmons 113 to be induced at theinterface between layer 104 and the interaction material 110. Plasmonsmay occur in other configurations. For example, if the real parts of thedielectric constants ε and ε′) of layer 104 and the interaction material110 have opposite signs at the interface, plasmons can be produced andone skilled in the art may find a number of configurations and materialconfigurations that establish these conditions.

The outer layer may, in one embodiment, comprise vanadium dioxide, whichis known to undergo an insulator-to-metal or semiconductor-to-metalphase transition at a certain temperature, as described in R. Lopez, L.A. Boatner, T. E. Haynes, L. C. Feldman, and R. F. Haglund, Jr.,“Synthesis and characterization of size-controlled vanadium dioxidenanocrystals in a fused silica matrix”, Journal of Applied Physics,Volume 92, Number 7, Oct. 1, 2002, which is incorporated herein byreference. By incorporating vanadium dioxide into the structure, theability to produce plasmons could be switched on or off depending on thetemperature of the material.

In the above description of the generation of plasmons in the waveguide,the plasmons are generated by a guided optical wave, typically throughtotal internal reflection or other guiding or partially guidingapproaches in a fiber. Other methods of coupling an electromagnetic waveto a plasmon are possible, some of which are described in W. L. Barnes,A. Dereux, and T. W. Ebbesen, “Surface plasmon subwavelength optics”,Nature, Volume 424, Aug. 14, 2003, 824-830, which is incorporated hereinby reference. These methods include and are not limited to prismcoupling, scattering from a topological defect on the surface on whichthe plasmon is to be generated, and periodic corrugation in the surfaceon which the plasmon is to be generated. These methods may be used togenerate plasmons at any point along the waveguide. FIG. 1 a showsplasmons occurring as surface plasmons at the interface between thelayer 104 and the interaction material 110, but plasmons may occur inother spatial locations. Plasmons may also occur at the interfacebetween the layer 104 and the inner material 103 of the waveguide, orthey may occur within a material. Plasmons are described in C. Kittel,“Introduction to Solid State Physics”, Wiley, 1995, which isincorporated herein by reference.

Generally, photocatalysis is the change in the rate of a chemicalreaction in the presence of electromagnetic energy. Many different typesof photocatalytic reactions exist. In some types of photocatalysis, theelectromagnetic energy directly interacts with the reagents (e.g., byraising a molecule to an excited state, thereby increasing itsreactivity). In other cases, the interaction is indirect, with theelectromagnetic energy activating an intermediate material which theninduces the desired reaction (e.g., by creating an electromagnetic pairin a semiconductor, leading to an activated reaction surface). Inphotocatalysis, the electromagnetic energy may directly supply thereaction's driving energy, or it may indirectly enable a self-energizedreaction (e.g., rhodopsin activated phototransduction in the eye). Moredetailed description of photocatalysis can be found in Masao Kaneko andIchiro Okura, “Photocatalysis: Science and Technology”, Springer-Verlag,2002; and photocatalytic properties and processes involving plasmons canbe found, for example, in P. V. Kamat, “Photoinduced transformation insemiconductor-metal nanocomposite assemblies”, Pure & Applied Chemistry,Volume 74, Number 9, 2002, pages 1693-1706; each of which isincorporated herein by reference.

A simplified example of a mechanism by which photocatalysis may occur isillustrated in FIG. 1 c, where electromagnetic energy 152 is incident ona photocatalyst 112. In the embodiment shown in FIG. 1 c, theelectromagnetic energy 152 may include energy in the form of a plasmon113 or in the form of radiated electromagnetic energy 115 as shown inFIGS. 1 a and 1 b, or it may include a combination of both. In the casewhere the electromagnetic energy 152 includes energy in the form of aplasmon 113, the electromagnetic energy may include a portion of theplasmon field that extends into the material 110 and/or a portion of theplasmon field that extends into the layer 104, or it may include adifferent portion of the plasmon field. The electromagnetic energy 152causes an electron 153 to move from the valence band 154 to theconduction band 156 of the photocatalyst 112, creating an electron-holepair, e− 158 and h+ 160.

The photocatalyst 112 may be chosen according to the frequency ofelectromagnetic energy 152 that is incident on it. For example, thephotocatalyst 112 may be chosen to be one having an energy gap betweenthe valence band 154 and the conduction band 156 corresponding to theenergy of the incident electromagnetic energy 152. Or, for a givenphotocatalyst 112, the energy of the incident electromagnetic energy maybe chosen to match the energy gap between the valence band 154 and theconduction band 156. As previously described, plasmon energy may bedelivered to the photocatalyst 112 by placing the photocatalyst 112substantially in the field of the plasmon 113, or it may also bedelivered to the photocatalyst 112 by causing the plasmon 113 to radiateelectromagnetic energy 115. A wide range of general applications ofphotocatalysis are described later in this application.

FIG. 1 d shows an embodiment where the waveguide 102 is an optical fiberthat does not have a conductive layer 104. In this embodiment, thewaveguide 102 includes an electromagnetic field 180 outside thewaveguide, where there exists a metal nanoparticle 182. Theelectromagnetic field 180 couples to plasmons 184 on the nanoparticle182, and the plasmons 184 on the nanoparticle 182 may deliver energy toa photocatalyst 112.

Creation of plasmons on a particle in an-electromagnetic field isdescribed in P. G. Kik, A. L. Martin, S. A. Maier, and H. A. Atwater,“Metal nanoparticle arrays for near field optical lithography ”,Proceedings of SPIE, 4810, 2002 which is incorporated herein byreference. Such a configuration may be useful, for example, inphotocatalytic lithography. In the embodiment shown in FIG. 1 d, thewaveguide 102 is an optical fiber and the electromagnetic field 180outside the fiber is created by a bend 186 in the fiber, such a bendbeing known to cause electromagnetic energy to leave the fiber. Thewaveguide 102 may, in other embodiments, be a different kind ofwaveguide, and electromagnetic energy 180 may be incident on thenanoparticle 182 from the waveguide 102 via ways other than a bend in afiber.

In one embodiment, shown in FIG. 2 a, a laser 202 that emitselectromagnetic energy in a first wavelength band provideselectromagnetic energy 204. Various methods exist for couplingelectromagnetic energy into a waveguide, and those skilled in the artwill be familiar with the various methods for guiding and couplingelectromagnetic energy. In the embodiment shown in FIG. 2 a, the emittedelectromagnetic energy 204 is reflected from a mirror 206 into thewaveguide 208 that, in turn, guides the electromagnetic energy 204 intoor near to a vessel 210 configured to hold an interaction material 212.The interaction material 212 may be any state of matter including butnot limited to a solid, liquid, gas, or plasma. The interaction materialbefore photocatalysis 212 is shown in FIG. 2 a and the interactionmaterial after photocatalysis 213 is shown in FIG. 2 b. Although FIGS. 2a and 2 b are drawn with a vessel 210, the vessel is not critical andthe waveguide may be configured to deliver energy to, for example,ground water or another environment in which the material that receivesenergy from the waveguide does not require a vessel.

Although a mirror 206 is shown here as an example of an optical elementthat may be used to direct energy into the waveguide, in some casesdifferent or additional optical elements may be used, such as lenses,polarizers, filters, or other elements, which may be used alone or incombination. Further, the preceding list refers to elements typicallyassociated with optical wavelengths of energy, and for other wavelengthbands different elements may be required for directing and focusing theenergy. Moreover, in various embodiments, the source of electromagneticenergy may be formed integrally with other elements, may be coupledevanescently to a waveguide, may be a pigtailed assembly, or may be anyother configuration for producing the appropriate coupledelectromagnetic energy. Moreover, although a single laser 202 ispresented in FIG. 2 a, more than one source of electromagnetic energymay be coupled to the waveguide 208. For example two or more lasers maybe coupled to the waveguide 208. Such lasers may be of a commonwavelength or may, in some configurations, have different wavelengths,depending upon various design considerations.

FIG. 2 a shows the source of electromagnetic energy being a laser 202that is outside the waveguide 208. In other embodiments the source ofelectromagnetic energy may be inside the waveguide 208, or there may bea source or sources outside the waveguide 208 and/or a source or sourcesinside the waveguide 208. Sources of electromagnetic radiation that maybe included in a waveguide are known to those skilled in the art, andmay include a microcavity semiconductor laser such as that described inU.S. Pat. No. 5,825,799, to Seng-Tiong Ho, Daniel Yen Chu, Jian-PingZhang, and Shengli Wu, which is incorporated herein by reference.

FIG. 2 c shows a case similar to that in FIG. 2 a, but whereelectromagnetic energy 204 is configured to travel some distance to theinteraction material 212. In one case, the electromagnetic energy isguided by a preliminary waveguide 214, where the preliminary waveguide214 may be an optical fiber configured to guide electromagnetic energyover distances of thousands of miles or more. The waveguide may becontinuous, where the preliminary waveguide 214 is substantially thesame as the waveguide 208, or, as shown in FIG. 2 c, the waveguide maybe discontinuous, and may possibly include elements such as the mirror206 shown in FIG. 2 c. In other embodiments, the preliminary waveguide214 may be configured to guide the electromagnetic energy over shorterdistances, for example, distances on the order of meters. In otherembodiments, there may be no preliminary waveguide 214, and theelectromagnetic energy may travel in free space to the waveguide 208.

In one embodiment, the electromagnetic energy is in the visible or UVportion of the electromagnetic spectrum. In this case, the waveguide maybe an optical fiber, an integrated waveguide, a polymeric waveguide, orany other waveguide suited for such energy. The optical fiber maycomprise a graded index of refraction or a step index of refraction, orthe optical fiber could be another of the many types of optical fibersknown to those skilled in the art. In the case of electromagnetic energyin the UV portion of the electromagnetic spectrum, the waveguide maycomprise quartz.

In another embodiment, the waveguide may comprise a photonic band-gapmaterial and/or a photonic band-gap like structure. One example of sucha guide may be found in S. A. Maier, P. E. Barclay, T. J. Johnson, M. D.Friedman, and O. Painter, “Low-loss fiber accessible plasmon waveguidefor planar energy guiding and sensing,” Applied Physics Letters, Volume84, Number 20, May 17, 2004, 3990-3992, which is incorporated herein byreference, where a waveguide is formed from a silicon membrane having atwo-dimensional pattern of gold dots patterned on one side of thesubstrate. The patterned gold dots constrain propagating electromagneticenergy to the silicon by forming a photonic band gap, and also allowplasmons to propagate along the array of gold dots. The size and spacingof the gold dots affect the guiding properties of the waveguide. Whilethe exemplary embodiment above implements a waveguide and plasmongenerator with a photonic bandgap material in a particular arrangement,a variety of other configurations employing photonic bandgap materialsmay be implemented. In some approaches the photonic bandgap structureand plasmon generating structure may be integral, while in otherapproaches, the photonic bandgap material may be arranged primary forguiding and a second structure can be combined to produce plasmonsresponsive to the guided energy.

In another embodiment, shown in FIG. 3 a, a source 302 produceselectromagnetic energy 304. Optical elements 306, 308 (in this case, aconverging lens 306 and a mirror 308) direct the energy to an array ofwaveguides 310. Although the array 310 in FIG. 3 is shown having sevenwaveguides, it may have any number of waveguides. A vessel 312 isconfigured to hold the array of waveguides 310 and a material 314 thatreacts with electromagnetic energy. Although FIG. 3 a is drawn with avessel 312, the vessel is not critical and the array of waveguides maybe configured to deliver energy to, for example, ground water or anotherenvironment in which the material that receives energy from the fibersdoes not require a vessel.

The waveguides in the array may be configured so that the distributionof energy near the waveguides depends on the separations 316 between thewaveguides (illustrated in FIG. 3 b). Such an energy dependence wasdemonstrated in J. P. Kottmann and O. J. F. Martin, “Plasmon resonantcoupling in metallic nanowires”, Optics Express, Volume 8, Number 12,Jun. 4, 2001; V. A. Podolskiy, A. K. Sarychev, and V. M. Shalaev,“Plasmon modes and negative refraction in metal nanowire composites”,Optics Express, Volume 11, Number 7, Apr. 7, 2003; S. A. Maier, M. L.Brongersma, P. G. Kik, and H. A. Atwater, “Observation of near-fieldcoupling in metal nanoparticle chains using far-field polarizationspectroscopy”, Physical Review B, Volume 65, page 193408; and V. A.Podolskiy, A. K. Sarychev, E. E. Narimanov, and E. M. Shalaev, “Resonantlight interaction with plasmonic nanowire systems”, Journal of Optics A,Volume 7, S32-S37, Jan. 20, 2005; each of which is incorporated hereinby reference.

For example, plasmon modes of waveguides were shown to interact undercertain conditions. Placing waveguides in relatively close proximity cancreate relatively high field strengths between the waveguides, so thereacting material 314 may be placed in the region where a high fieldstrength is expected to induce or speed up a reaction. Further, theplasmon modes (spatial distribution and excitation frequency) may be afunction of the number, type, and separation of the plasmon waveguides,so the location, distribution, and/or type of the reacting material 314may be chosen according to the modes excited in the array. The array maybe a random array, possibly characterized by an average separation 316between waveguides, or it may be a substantially ordered array, possiblyhaving separations 316 between waveguides characterized by amathematical formula. Although the references above describe plasmons ona wire or arrays of conducting dots, plasmons on different kinds ofwaveguides, such as a metal-coated fiber, may also interact. Further,although FIGS. 3 a and 3 b show the waveguides not touching, crossing,joining, or intersecting, in some embodiments it may be desirable forthe waveguides to be non-parallel, and the waveguides may in some casestouch, cross, join, or intersect, depending on the particular design.

In some embodiments, the waveguide may be completely coated with aconductor, as shown in FIG. 1. However, it may be desirable in otherembodiments to only partially cover the waveguide with a conductor, asshown in FIG. 4. In the embodiment shown in FIG. 4, electromagneticenergy 404 is directed into the waveguide 406. A portion of thewaveguide 406 is covered with a conductor 402, and surface plasmons maybe created on the surface of the conductor 402. Although FIG. 4 shows awaveguide having a single portion of the waveguide coated with aconductor, in other embodiments more than one portion of the waveguidemay be coated with a conductor.

FIGS. 1 a and 1 b show examples of configurations in which aphotocatalyst 112 is near the outer surface 108 of the conductive layer104. It may also be possible for the photocatalyst 112 to be joined tothe waveguide 102. FIG. 5 shows a waveguide 102 having a conductivelayer 104, a dielectric layer 501 in intimate contact with theconductive layer 104, and a photocatalyst layer 502 in intimate contactwith the dielectric layer 501. FIG. 5 shows the dielectric layer 501 andthe photocatalyst layer 502 as being continuous, but this need not bethe case and in some cases the conductive layer 104, the dielectriclayer 501, and/or the photocatalyst layer 502 may only partially coverthe waveguide, possibly in a periodic or semi-periodic array. Thethicknesses and materials of the layers 104, 501, and 502 may be chosento produce plasmons in the layer 501 that interact with thephotocatalyst layer 502. The layer 501 is described as a dielectriclayer, however in a different configuration the layers 104 and 501 maybe a different combination of materials for which plasmons exist at theinterface, as previously described.

In an arrangement shown in FIG. 6, the configuration may be used todeliver energy to a location, such as a location containing aphotocatalyst 112, using a waveguide. In this approach a set of gratings602, 604 are positioned beside a sub-wavelength aperture 606 in aconductive layer 607. As described for example in A. Degiron and T. W.Ebbeson, “The role of localized surface plasmon modes in the enhancedtransmission of periodic subwavelength apertures”, Journal of Optics A:Pure Applied Optics, Volume 7, Jan. 20, 2005, pages S90-S96,incorporated herein by reference, such gratings can produce plasmons 113that then couple through an aperture 606 and thereby increase throughputof electromagnetic energy 608 through the aperture 606. By integratingthis configuration with a waveguide 610, energy can couple from thewaveguide to locations outside of the waveguide.

FIG. 6 is shown with only one aperture in the conductive layer 607,however it may be desirable to have more than one aperture 606 in theconductive layer 607. In one approach, each of a plurality of aperturesis surrounded by respective gratings 602, 604. Further, the gratings602, 604 are shown having four periods, but the number of periods maydepend on the particular application. As described in Degiron, thewavelength(s) corresponding to the maximum transmission of energythrough the aperture 606 may depend on the period 612 of the gratings602, 604, the dielectric constant of the gratings 602, 604, and thedielectric constant of the surrounding materials 110, 614. The gratings602, 604, although shown only on the interface between the conductivelayer 607 and the material 614, may be on the interface between theconductive layer 607 and the material 110, or they may be on bothinterfaces. The gratings 602, 604 may have periodic variations that aresubstantially parallel to each other, or the gratings 602, 604 mayextend radially from the aperture 606. The aperture 606 is described asbeing sub-wavelength, but transmission of energy 608 may occur inconfigurations having apertures that are equal to or larger than thewavelength of transmitted energy 608. Although a photocatalyst 112 isshown as receiving the energy from the aperture 606, it may be desirablefor another type of material to react with the energy.

In an arrangement shown in FIG. 7, a waveguide 704 such as an opticalfiber or a 2d dielectric slab may include a patterned array ofconductive material 706. In FIG. 7, the conductive material isconfigured with spacings 708 wherein the spacings are separated by adistance 710.

A patterned array of conducting material having an array of holes thatare smaller than the wavelength of energy incident on them may haveenhanced transmission of this energy through the holes, as described inW. L. Barnes, W. A. Murray, J. Dintinger, E. Devaux, and T. W. Ebbesen,“Surface Plasmon Polaritons and Their Role in the Enhanced Transmissionof Light through Periodic Arrays of Subwavelength Holes in a MetalFilm”, Physical Review Letters, Volume 92, Number 10, Mar. 9, 2004, page107401; S. C. Hohng, Y. C. Yoon, D. S. Kim, V. Malyarchuk, R. Müller,Ch. Lienau, J. W. Park, K. H. Yoo, J. Kim, H. Y Ryu, and Q. H. Park,“Light emission from the shadows: Surface plasmon nano-optics at nearand far fields”, Applied Physics Letters, Volume 81, Number 17, Oct. 21,2002, pages 3239-3241; each which is incorporated herein by reference. Awaveguide having such an array may therefore have enhanced transmissionat certain wavelengths through the array 706. The wavelengthscorresponding to enhanced transmission, as described in Hohng, maydepend on the materials 712, 110 bordering the array. In FIG. 7 thearray 706 is shown extending along the entire length of the waveguide704, but in other configurations the array may extend over only aportion of the waveguide 704. The spacings 708 are described as beingsub-wavelength, but transmission of energy 716 may occur inconfigurations having apertures that are larger than the wavelength oftransmitted energy 716.

Although FIG. 7 shows a patterned array of conductive material 706, inanother embodiment the dimension of the inner material 712 may beconfigured to vary, possibly in a periodic or semi-periodic way. Thevariations may produce a surface having substantially square-wavevariations similar to that shown in FIG. 7, or the variations mayproduce a different kind of pattern such as a substantially sine-wavevariation or another kind of variation. In such an embodiment, theconductive material 706 may also have a thickness that varies, possiblyperiodically or semi-periodically, or the conductive material 706 mayhave a substantially uniform thickness.

Plasmons may be produced on a boundary between two materials when thereal parts of their dielectric constants ε and ε' have different signs,such as in areas where the conductive layer 104 and the material 110 arein contact. For example, in the periodic or semiperiodic arrangementshown in FIG. 7, plasmon energy can interact with the interactionmaterial 110 in a corresponding periodic or semiperiodic pattern.Moreover, in configurations such as those shown in FIGS. 4 and 6 it maybe possible to produce plasmons or electromagnetic energy in a definedspatial extent. These configurations may allow plasmon energy to bedistributed through a reaction area in a selected pattern, and mayproduce localized reactions, may produce reactions that have asymmetricspatial patterns, or may catalyze a reaction in a distributed fashion.Moreover, in configurations where plasmons are produced in defined areasalong the waveguide, the energy may propagate further and/or with lessdissipation in the guide than in configurations where the energy isconverted to plasmons along the entire length of the waveguide.

Such targeted spatial distributions of plasmons and/or electromagneticenergy may be useful, for example, in photocatalytic lithography, asdescribed in J. P. Bearinger, A. L. Hiddessen, K. J. J. Wu, A. T.Christian, L. C. Dugan, G. Stone, J. Camarero, A. K. Hinz and J. A.Hubbell, “Biomolecular Patterning via Photocatalytic Lithography”, inNanotech, 2005 Vol. 1,“Technical Proceedings of the 2005 NSTINanotechnology Conference and Trade Show, Volume 1”, Chapter 7: DNA,Protein, Cells and Tissue Arrays; and in Jae P. Lee and Myung M. Sung,“A new patterning method using photocatalytic lithography and selectiveatomic layer deposition”, Journal of the American Chemical Society,Volume 126, Number 1, Jan. 14, 2004, pages 28-29, each of which isincorporated herein by reference. Targeted spatial distributions ofplasmons and/or electromagnetic energy may also be useful inapplications where the interaction material 110 is distributed in anarray, where the interaction material 110 may comprise different kindsor different amounts of material in different parts of the array, orwhere it is desired to control the amount of energy delivered to thematerial 110 according to spatial position.

In general, photocatalysis has many applications and the embodimentsshown in FIGS. 1-7 have a wide variety of applications. Someapplications of photocatalysis are described in Akira Fujishima,“Discovery and applications of photocatalysis—Creating a comfortablefuture by making use of light energy”, Japan Nanonet Bulletin, Issue 44,May 12, 2005, which is incorporated herein by reference. These includethe extraction of hydrogen from water for use as a clean energy source,oxidation of materials (potentially for disinfection and deodorizationor for cleanup of toxic sites), and creating surfaces with“superhydrophilicity” and self-cleaning properties. A wide range ofapplications is detailed in Fujishima, and one skilled in the art mayapply the embodiments shown in FIGS. 1-7 to applications ofphotocatalysis, including those applications described above anddetailed in Fujishima. For example, the photocatalyst layer 502 in FIG.5 may include titanium dioxide and the material 110 may, in oneembodiment, be water, where the photocatalytic process is designed toremove impurities in the water.

Some of the embodiments in FIGS. 1-7 include materials that arepatterned, potentially on the nanoscale. For example, FIG. 7 shows ametal grating having a periodicity that may be fabricated usingtechniques such as lithography and/or deposition of material. Suchtechniques are known to those skilled in the art and may producefeatures having sizes on the order of nanometers or possibly less. Thesetechniques may be used to fabricate features in a regular array, adesired pattern, or a single defect. In the case of a single defect, thesize of the defect may be on the order of a nanometer, as described inKik.

In this disclosure, references to “optical” elements, components,processes or other aspects, as well as references to “light” may alsorelate in this disclosure to so-called “near-visible” light such as thatin the near infrared, infra-red, far infrared and the near and farultra-violet spectrums. Moreover, many principles herein may be extendedto many spectra of electromagnetic radiation where the processing,components, or other factors do not preclude operation at suchfrequencies, including frequencies that may be outside ranges typicallyconsidered to be optical frequencies.

The foregoing detailed description has set forth various embodiments ofthe devices and/or processes via the use of block diagrams, diagrammaticrepresentations, and examples. Insofar as such block diagrams,diagrammatic representations, and examples contain one or more functionsand/or operations, it will be understood as notorious by those withinthe art that each function and/or operation within such block diagrams,diagrammatic representations, or examples can be implemented,individually and/or collectively, by a wide range of hardware,materials, components, or virtually any combination thereof.

Those skilled in the art will recognize that it is common within the artto describe devices and/or processes in the fashion set forth herein,and thereafter use standard engineering practices to integrate suchdescribed devices and/or processes into elements, processes or systems.That is, at least a portion of the devices and/or processes describedherein can be integrated into optical, RF, X-ray, or otherelectromagnetic elements, processes or systems via a reasonable amountof experimentation.

Those having skill in the art will recognize that a typical opticalsystem generally includes one or more of a system housing or support,and may include electrical components, alignment features, one or moreinteraction devices, such as a touch pad or screen, control systemsincluding feedback loops and control motors (e.g., feedback for sensinglens position and/or velocity; control motors for moving/distortinglenses to give desired focuses). Such systems may include imageprocessing systems, image capture systems, photolithographic systems,scanning systems, or other systems employing optical, RF, X-ray or otherfocusing or refracting elements or processes.

While particular embodiments of the present invention have been shownand described, it will be understood by those skilled in the art that,based upon the teachings herein, changes and modifications may be madewithout departing from this invention and its broader aspects and,therefore, the appended claims are to encompass within their scope allsuch changes and modifications as are within the true spirit and scopeof this invention. Furthermore, it is to be understood that theinvention is solely defined by the appended claims. It will beunderstood by those within the art that, in general, terms used herein,and especially in the appended claims (e.g., bodies of the appendedclaims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”“comprise” and variations thereof, such as, “comprises” and “comprising”are to be construed in an open, inclusive sense, that is as “including,but not limited to,” etc.). It will be further understood by thosewithin the art that if a specific number of an introduced claimrecitation is intended, such an intent will be explicitly recited in theclaim, and in the absence of such recitation no such intent is present.For example, as an aid to understanding, the following appended claimsmay contain usage of the introductory phrases “at least one” and “one ormore” to introduce claim recitations. However, the use of such phrasesshould not be construed to imply that the introduction of a claimrecitation by the indefinite articles “a” or “an” limits any particularclaim containing such introduced claim recitation to inventionscontaining only one such recitation, even when the same claim includesthe introductory phrases “one or more” or “at least one” and indefinitearticles such as “a” or “an” (e.g., “a” and/or “an” should typically beinterpreted to mean “at least one” or “one or more”); the same holdstrue for the use of definite articles used to introduce claimrecitations. In addition, even if a specific number of an introducedclaim recitation is explicitly recited, those skilled in the art willrecognize that such recitation should typically be interpreted to meanat least the recited number (e.g., the bare recitation of “tworecitations,” without other modifiers, typically means at least tworecitations, or two or more recitations).

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 20. Thesystem of claim 27 wherein the plasmon generator includes a structurepatterned to produce plasmons.
 21. (canceled)
 22. The system of claim 20wherein the structure patterned to produce plasmons includes a grating.23. The system of claim 20 wherein the structure patterned to produceplasmons includes an array of nanoparticles.
 24. The system of claim 23wherein the array of nanoparticles is configured to deliver energy to aresist.
 25. The system of claim 23 wherein the array is a substantiallyregular array.
 26. (canceled)
 27. A system comprising: A firstwaveguide, said first waveguide being configured to carry energy from afirst location to a second location, said first waveguide including afirst inner region and a first outer region, said first outer regionhaving a first outer surface; A plasmon generator coupled to said firstwaveguide and operative to produce plasmons; and An interaction materialproximate to said second location and responsive to said plasmons toreact chemically.
 28. (canceled)
 29. (canceled)
 30. The system of claim27 further including a second material in intimate contact with thefirst outer surface, wherein the second material includes theinteraction material.
 31. (canceled)
 32. (canceled)
 33. (canceled) 34.The system of claim 27 wherein the interaction material includes aphotocatalyst, and wherein the photocatalyst includes a semiconductor.35. The system of claim 27 wherein the first outer surface is configuredto support the plasmons.
 36. (canceled)
 37. The system of claim 27wherein the first outer region covers a portion of the first innerregion.
 38. The system of claim 27 wherein the thickness of the firstouter region varies.
 39. (canceled)
 40. The system of claim 27 whereinthe thickness of the first inner region varies.
 41. The system of claim40 wherein the thickness of the first inner region varies substantiallyperiodically.
 42. The system of claim 38 wherein the first outer regionhas periodic defects of material, said defects having a width, whereinthe thickness of the first outer region is substantially zero at theposition of the defects.
 43. The system of claim 42 wherein the plasmonsare configured to have an energy band, and wherein said energy band is afunction of the width of the defects.
 44. (canceled)
 45. The system ofclaim 27 wherein the first outer region includes a metal.
 46. (canceled)47. The system of claim 45 wherein the metal includes silver.
 48. Thesystem of claim 45 wherein the metal includes copper.
 49. The system ofclaim 27 wherein the first outer region includes an aperture.
 50. Thesystem of claim 49 wherein the first outer region includes a conductor.51. The system of claim 50 wherein the first outer region includes ametal.
 52. The system of claim 49 wherein the first outer regionincludes a grating structure proximate to the aperture.
 53. (canceled)54. The system of claim 27 wherein the first outer region includesvanadium dioxide.
 55. (canceled)
 56. (canceled)
 57. (canceled) 58.(canceled)
 59. (canceled)
 60. (canceled)
 61. (canceled)
 62. (canceled)63. (canceled)
 64. (canceled)
 65. (canceled)
 66. (canceled) 67.(canceled)
 68. (canceled)
 69. (canceled)
 70. A system comprising: Afirst waveguide, said first waveguide being configured to carry energyfrom a first location to a second location, said first waveguidecomprising an optical fiber; A plasmon generator coupled to said firstwaveguide; and An interaction material proximate to said second locationand responsive to plasmons to react chemically.
 71. The system of claim70 wherein the optical fiber includes a gradient index of refraction.72. The system of claim 70 wherein the optical fiber includes adiscontinuous index of refraction.
 73. The system of claim 70 whereinthe optical fiber includes quartz.
 74. (canceled)
 75. A systemcomprising: A first waveguide, said first waveguide being configured tocarry energy from a first location to a second location, said waveguideincluding a conductor configured to carry terahertz energy; A plasmongenerator coupled to said first waveguide; and An interaction materialproximate to said second location and responsive to plasmons to reactchemically.
 76. A system comprising: A first waveguide, said firstwaveguide being configured to carry energy from a first location to asecond location, said first waveguide including a photonic band gapmaterial; A plasmon generator coupled to said first waveguide; and Aninteraction material proximate to said second location and responsive toplasmons to react chemically.
 77. A system comprising: A firstwaveguide, said first waveguide being configured to carry energy from afirst location to a second location, said first waveguide beingconfigured to support electromagnetic energy in a first wavelength band;A plasmon generator coupled to said first waveguide; and An interactionmaterial proximate to said second location and responsive to plasmons toreact chemically.
 78. The system of claim 77 wherein the firstwavelength band includes infrared wavelengths.
 79. The system of claim77 wherein the first wavelength band includes visible wavelengths. 80.The system of claim 77 wherein the first wavelength band includesultraviolet wavelengths.
 81. The system of claim 77 wherein the firstwavelength band includes microwave wavelengths.
 82. (canceled) 83.(canceled)
 84. (canceled)
 85. (canceled)
 86. (canceled)
 87. (canceled)88. (canceled)
 89. (canceled)
 90. (canceled)
 91. (canceled) 92.(canceled)
 93. (canceled)
 94. (canceled)
 95. (canceled)
 96. (canceled)97. (canceled)
 98. (canceled)
 99. (canceled)